Download Organic Metal and Metalloid Species in the Environment

Organic Metal and Metalloid Species in the Environment
Analysis, Distribution, Processes and Toxicological Evaluation
Bearbeitet von
Alfred V. Hirner, Hendrik Emons
1. Auflage 2004. Buch. XVIII, 328 S. Hardcover
ISBN 978 3 540 20829 7
Format (B x L): 15,2 x 23,5 cm
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Chapter 1
Organometallic compounds in the environment:
An overview
P. J. Craig and R. O. Jenkins
General points
In this chapter organometallic compounds are defined as those which have a carbon to metal single sigma bond polarized Mδ+ - Cδ- (some useful sources are listed
in the References Craig 2003; Abel et al. 1995; Bennett et al. 1994, Crompton
2002; Ebdon et al: 2001; Elschenbroich and Salzer 1992; Sigel and Sigel 1993;
Hock 2001; Ure and Davidson 1995). The metals of interest are usually main
group metals in environmental matters (They are shown in Tables 1 and 2). For
useful information to be derived, these substances need to be analysed. In most
cases a full speciation analysis is not possible; the organometallic fragment is usually bound to a complex environmental moiety which may not be identifiable.
Nevertheless much progress in speciation analysis has been made in recent years
(see references above). For speciation analysis in the environment to be possible
the organometallic fragment has to be separated from its environmental binding
and then measured.
(i)
Methods of Separation
a.
b.
c.
d.
e.
f.
(ii)
Gas chromatography
Thermal desorption methods
High performance liquid chromatography
Flow injection methods
Ion exchange chromatography
Ion chromatography
Methods of Detection
a.
b.
c.
d.
e.
f.
Atomic absorption spectroscopy
Atomic fluorescence spectroscopy (sometimes with hydride
generation)
Atomic emission spectroscopy
Voltammetry
Mass spectrometry
X-ray and neutron methods
2
Craig and Jenkins
Table 1. Stability of methylmetals to oxygen a
Stable
Unstable b
Me2Hg
MePbX3
Me4Si, [Me2SiO]n, (Me)nSi(4-n)+, Me6Si2
MeTI+
Me4Ge,Me4Ge(4 n)+, Me6Ge2
Me2Zn, MeZn+
Me2Cd, MeCd+
Me4Sn
Me4Pb§
Me3B
MeHgX (Ph and Et also stable)
Me3Al
Me4 nSnXn
Me3Ga
Me3In
Me3PbX
Me2PbX2
Me3Tl
Me(C5H4)Mn(CO)3 c
Me3As e
MeMn(CO)4L d
Me3Sb e
Me2AsO(OH)
Me3Bi e
Me2AsH
MeAsO(OH)2
Me2S
MeAsX2
Me2Se
MeSbX2
Me4nSnHn e
MeHgSeMe
MeCoB12 (solid state)
Me6Sn2 (At RT gives [Me3Sn]2O)
Me3SbO
Me6Pb2 (to methyl lead products)
Me2SbO(OH)
Me3Sb
MeSbO(OH)2
Me3AsO
Me3P
Me2Tl+, Me2Ga+
Me3S+
Me4SiH4-n
Me3Se+
Me4GeH4-n
Me3PO
a
At room temperature in bulk as against rapid (seconds, minutes) oxidation.
Assume similar but lesser environmental stability for ethyls.
b
Variously unstable because of empty low lying orbitals on the metal, polar metalcarbon bonds and/or lone electron pairs on the metal.
c
Gasoline additive.
d
To exemplify ligand-complexed transition metal organometallics. Many of these
synthetic compounds are oxygen-stable but none have been found in the natural
environment.
e
But stable in dilute form and detected in the environment
Reproduced in part from Craig (2003) with permission
Organometallic compounds in the environment: An overview
3
Table 2 Stability of organometallic species to water
Organometallic
R2Hg, R4Sn, R4Pb
Stability, comments
Only slightly soluble, stable, diffuse to atmosphere. Higher alkyls
less stable and less volatile. Species generally hydrophobic and
variously volatile
MeHgX
Stable, slightly soluble depending on X
Soluble, methyltin units stable but made hexa- and penta(Me)nSn(4-n)+
coordinate by H2O, OH-. Species are solvated, partly hydrolysed
to various hydroxo species. At high pH polynuclear bridged hydroxo species form for (Me)2Sn2+
+
Me3Pb
Soluble, hydrolysis as methyltins above. Also dismutates to
Me4Pb and Me2Pb2+ at 20 oC
Me2Pb2+
Soluble as for Me3Pb+ above. Disproportionates to Me3Pb+ and
CH+3 slowly. These reactions cause eventual total loss of Me3Pb+
and Me2Pb2+ from water.
Me2As+
Hydrolyses to Me2AsOH then to slightly soluble [Me2As]2O
Hydrolyses to MeAs(OH)2 then to soluble (MeAsO)n
MeAs2+
Stable and soluble (330 g dm-3). Acidic pKa = 6.27. i.e. cacodylic
Me2AsO(OH)
acid, dimethylarsinic acid. Detected in oceans
MeAsO(OH)2
Stable and soluble. Strong acid pK1 = 3.6, pK2 = 8.3 – methylarsonic acid. Detected in oceans
Me3S+, Me3Se+
Stable and slightly soluble
Hydrolyse and condense, but methylsilicon groups retained
MenSlCl4-n
Stable, soluble, has been discovered in oceans. Hydrolyses but
MenGe(4-n)+
MenGe moiety preserved
Very stable, soluble, but not been detected as a natural environMe2Tl+
ment product
Me3AsO, Me3SbO
Stable and soluble
Insoluble, diffuses to atmosphere, air unstable
MeAsH, CH3AsH2
MeSbO(OH)
Stable and soluble. Detected in oceans
CH3SbO(OH)2
Stable and soluble. Detected in oceans
Solubility refers to air-free distilled water, no complexing ligands. Range of solubility is
from mg dm-3 to g dm-3.
Other species
Stable and insoluble – R4Si, (R2SiO)n,H3HgSeCH, most PhHg derivatives, Me2S, Me2Se,
Me4Ge, Me3B
Unstable – MePb+ (has not been detected in the environment), R2Zn, R2Cd, R3Al, R3Ga,
Me6Sn2, Me6Pb2, MeTl2+, MeCd+, Me2Cd, Me2Sb+, MeSb2+.
Reproduced in part from Craig (2003) with permission
4
Craig and Jenkins
Separation and detection of organometallics in the environment presupposes
that the species are stable. Stability is not discussed here but it is discussed in detail in a recent work (Craig 2003). Toxicology is also covered elsewhere in this
work.
As many organometallic moieties are tightly bound in the environment, they
may not be volatile and susceptible to separation as above. For such cases separation by derivatization is usually carried out.
This is generally achieved by (formal) SN2 attack by hydride (from NaBH4),
ethyl (NaBEt) or other alkyl group (e.g. from a Gignard reagent), e.g. (Eqn. 1)
NaBH4
Bu 3SnX
→ Bu 3SnH
[1]
X = environmental counter ion
Organometallic compounds may be found in the natural environment because
they are formed or because they are introduced. The chemistry of the latter group
is better known, and their environmental impact has been widely discussed. Organometallic compounds introduced to the environment directly may enter via use
as products whose properties relate to the environment (e.g. biocides) or they may
enter additionally to a separate, main function (e.g. gasoline additives, polymer
stabilizers). Compounds of arsenic, mercury, tin and lead have important environmental roles as organometallic compounds.
Where organometallics are formed in the environment it is usually as a result of
a methylation process, “biomethylation”. This process is discussed below.
As mentioned above, stabilities will be little discussed here (but are shown in
Tables 1 and 2), but it should be pointed out that the metal carbon bond is not necessarily weak (i.e. leading to decay for thermodynamic reasons), but there are often low energy routes for metal-carbon decomposition (i.e. kinetic decay). In the
latter case the activation energy for decay is low.
In a similar way, all organometallic compounds are thermodynamically unstable to oxidation because of the lower free energies of the products of oxidation.
However, some do not oxidise (or are not inflammable) for kinetic reasons. Compounds which in bulk may e.g. ignite are sometimes stable at high attenuation.
Most organometallics are thermodynamically unstable to hydrolysis to the metal
hydroxide and hydrocarbon. Again many are kinetically stable e.g. if nucleophilic
attack by water on the metal cannot take place because lack of suitable orbitals on
the metal or if the attack is physically blocked by ligands.
Stability to light for organometallics is most important for those volatile species
which enter the atmosphere, and less relevant for those coordinated to biological
or environmental ligands in organisms or water. Chemistry, decay and toxicity of
organometallic species in biological systems is discussed elsewhere (see above)
and in the present work.
Organometallic compounds in the environment: An overview
5
Biomethylation
Biomethylation is the process whereby living organisms produce a direct linkage
of a methyl group to a metal or metalloid, thus forming metal-carbon bonds. Methylation has been extensively studied and biomethylation activity has been found
in soil, but mainly occurs in sediments in e.g. estuaries, harbours, rivers, lakes and
oceans. The addition of a methyl group to a metall(oid) changes the chemical and
physical properties of that element, and this then influences toxicity. The organisms responsible for metall(oid) biomethylation are nearly all microorganisms.
Anaerobic bacteria are believed to be the main agents of biomethylation in sediments and other anoxic environments. Some aerobic and facultatively anaerobic
bacteria, as well as certain fungi and lower algae, may also methylate metals. With
the exception of vitamin B12 higher organisms, containing a methyl-cobalt bond,
do not seem to be able to methylate genuine metals. The situation is different for
the metalloids arsenic, selenium and tellurium: many higher organisms have been
shown to form methyl derivatives of these elements, e.g. methylarsenicals are
formed in a wide range of organisms, including marine biota and mammals (and
man).
Volatile methyl and hydride derivatives of metal(loids) can often be found in
gases released from natural and anthropogenic environments (Feldmann and Hirner 1999; Feldmann et al. 1999; Hirner et al. 1998; Feldmann et al. 1994), e.g.
geothermal gases, sewage treatment plants, marine sediments, landfill deposits),
and biological production of volatile compounds is believed to be an important
part of the biogeological cycles of metal(loids)s, such as arsenic, mercury, selenium and tin. With the exception of arsenic and selenium (and perhaps antimony),
biomethylation increases toxicity, because methyl derivates are more lipophilic
and therefore more biologically active.
Biomethylation of organic molecules – e.g. such as proteins, nucleic acid bases,
polysaccharides and fatty acids – occurs in all living cells and is an essential part
of normal intracellular metabolism. The three main biological methylating agents
for organic molecules – S-adenosylmethionine (SAM), methylcobalamine and Nmethyltetrahydrofolate – have all been shown to be capable of involvement in the
biomethylation of metall(oids). SAM is a ubiquitous methylating agent and is synthesised by the transfer of an adenosyl group from ATP to the sulphur atom of methionine.
A positive charge on the sulphur atom activates the methyl group of methionine, making SAM a methyl carbonium ion donor. The methyl group in biochemistry is transferred as a radical (CH3•) or as a carbonium ion (CH3+) and the atom receiving the methyl group must be nucleophilic, which requires a lone pair of
electrons in the metal valency shell; i.e. oxidative addition, where there is alternation of Mn+ and M(n+2)+ oxidation states. The reaction (involving carbonium ions)
is usually referred to as the Challenger mechanism, devised originally to account
for the methylation of arsenic (Challenger et al. 1933; Brinckman and Bellama
1978) (Figure 1). SAM has subsequently been shown also to be the methylating
agent for selenium, tellurium, phosphorus (Fatoki 1997) and antimony (Andrewes
6
Craig and Jenkins
et al. 1999a), all of which have lone paid of electrons. N-Methyltetrahydrofolate
like SAM, is thought to transfer methyl groups as carbonium ions or an intermediate radical, but its transfer potential is not as high as SAM. Conversely, for methylcobalamin in the environment – a derivative of vitamin B12 – the methyl group
is transferred as a carbanion (CH3-) and the recipient atoms must be electrophilic
e.g. mercury (II). Methylcobalamin is well established as a methylating agent for
mercury and can also be involved in (in vitro) methylation for lead, tin, palladium,
platinum, gold and thallium (Fatoki 1997). Although methylcobalamin appears to
be the only carbanion methylating agent, in the natural environment, a carbanion
may also be transferred to metals from other organometallic species which may be
present, e.g. Me3Pb+, Me3Sn+. Regardless of the methylating agent, only one
methyl group transfers to the metal(loids) in each step, although further groups
may then be transferred to the same receiving atom. Methylation of some individual elements is now discussed.
Arsenic
Many microorganisms can methylate arsenic and methylarsenic compounds are
produced, under both aerobic and anaerobic conditions (Cullen and Reimer 1989).
Fungal methylation of arsenic was reported in the nineteenth century, when several poisoning incidents in England and Germany were associated with arsenic
containing wall papers. Gosio in 1901, reported that a garlic-smelling, methylated
arsenic compound was released from moulds growing in the presence of inorganic
arsenic. Challenger et al. (1933) identified this as trimethylarsine (Me3As). Several
fungi have been shown to methylate arsenic under aerobic conditions, including
Scopulariopsis brevicaulis, Penicillium sp., Gliocladium roseum and the yeast
Cryptococcus humicola (Brinckman and Bellama 1978; Thayer 1984; Andreae
1986). The mechanism of arsenic methylation in fungi was established by Challenger et al 1933 and involves a series of reductions and oxidative methylations,
using SAM (Figure 1.) as a methyl donor.
Organometallic compounds in the environment: An overview
7
Fig. 1. Arsenic methylation according to the Challenger mechanism
Certain bacteria have also been shown to methylate arsenic under aerobic conditions, including Flavobacterium sp., Escherichia coli and Aeromonas sp.
(Thayer 1984).
Arsenic biomethylation can also be catalysed by obligate anaerobic bacteria,
e.g. Methanobacterium sp. can reduce AsO3- to AsO2-, with subsequent methylation to methylarsonic acid, dimethylarsenic acid and dimethylarsine (Takahashi et
al. 1990). Methylcobalamin is the methyl donor for arsenic methylation by
methanogenic archaea (McBride and Wolfe 1971). Michalke et al. (2000) have reported trimethylarsine in the gas phase above anaerobic cultures of Methanobacterium formicicum, Clostridium collagenovorans and two Desulfovibrio spp. For C.
collagenovorans and D, vulgaris, trimethylarsine was the only volatile arsenic
species detected. Conversely, M. formicicum volatilised arsenic as mono- di- and
trimethylarsine and as arsine (AsH3), while Methanobacterium thermoautotrophicum produced only arsine. This data serves to illustrate the key role of the organism for metal(loid) microbial transformations.
There is an extensive marine chemistry for arsenic with many methylarsenic riboside species identified and analogous compounds are now being found in terrestrial situations.
8
Craig and Jenkins
Antimony
Mono- and dimethylantimony species have been found to be formed in both marine and terrestrial natural waters (Andreae 1981; Andreae 1984). Freshwater
plants from two lakes contaminated by mine effluent, and plant material from an
abandoned antimony mine have also been shown to contain methylantimony species (Craig et al. 1999; Dodd et al. 1996).
Biomethylation of inorganic antimony by the aerobic fungus Scopulariopsis
brevicaulis is documented (Craig et al. 1998; Jenkins et al. 1998a; Jenkins et al.
1998b; Andrewes et al. 1998; Andrewes et al. 1999b; Andrewes et al. 2000) and is
thought to involve methyl transfer via SAM (Andrewes et al. 1999a). Recently,
the fungus Phaeolus schweinitzii has also been shown able to biomethylate antimony (Andrewes et al. 2001). Mixed cultures of bacteria growing under anaerobic
conditions have been shown to generate volatile trimethylantimony as the sole
volatilised antimony species (Gates et al. 1997, Gurleyuk et al 1997, Jenkins et al
1998c). Volatilisation of antimony from environmental sediments and municipal
waste sites also suggests that certain anaerobic and/or facultatively anaerobic bacteria can biomethylate (Hirner et al. 1994; Feldmann et al. 1994) antimony. Michalke et al. (2000) reported biomethylation of inorganic antimony by pure cultures of anaerobic bacteria. C. collagenovorans, D. vulgaris and three species of
methanogenic archaea, were shown to produce trimethylantimony in culture headspace gases. M. formicium was shown to produce SbH3 together with Me3-nSbHn
(n = 0,72) into culture headspace gases.
Mercury
Biomethylation of mercury has been studied extensively. Methylation of mercury
increases lipid solubility and thus enhances bioaccumulation in living organisms.
This can lead to mercury entering the food chain and to mercury poisoning incidents, e.g. in Japan and Iraq (Craig 2003). Many different bacteria in aerobic and
anaerobic environments are known to cause mercury biomethylation, although anaerobic sediments are the main sites of environmental methylmercury formation
(Fatoki 1997). Sulphur-reducing bacteria, such as Desulfovibrio desulfuricans, are
thought to be the most important methylators of mercury (Compeau and Bartha
1985; Compeau and Bartha 1987; Kerry et al. 1991). Both low pH and high sulfate
concentrations promote mercury biomethylation activity within environmental
sediments (Winfrey and Rudd 1990; Craig and Moreton 1984). Methylcobalamin
is the methyl donor, giving rise to monomethylmercury and (in a slower step) dimethylmercury (volatile) products in a transfer to electrophilic mercury (II) of a
methyl carbonium ion (Eqn 2) viz.
H 2O
CH 3CoB12 + Hg 2+ 
→ CH 3 Hg + + H 2OCoB12
[2]
Organometallic compounds in the environment: An overview
9
Further reaction of methylmercury can occur via various biotic mechanisms
(e.g. disproportionation reaction involving H2S) also giving rise to dimethylmercury (Eqn 3) (Craig and Moreton 1984).
2CH 3 Hg + + S 2− → (CH 3 Hg ) 2 S → (CH 3 ) 2 Hg + HgS [3]
An important factor governing the concentration of mercury in biota is the concentration of methyl mercury in environmental waters, which is determined by the
relative efficiencies of methylation and demethylation processes.
Several other metals and metalloids can undergo methylation and these systems
have been discussed in detail in a recent work (Craig 2003). The elements involved include tin, bismuth, selenium and others. An example of a biogeochemical
cycle for tin is shown in Figure 2.
Fig. 2. The biogeochemical cycle of tin
(TBT use)
Bu3SnX
Inorg Sn / Rn SnX4-n
BunSnH4-n
BunSnMe4-n
BuMe3Sn
Bu2Me2Sn
Bu3MeSn
BunSnH4-n
BuSn2+
Bu3Sn+
Me2Sn2+
Bu2Sn2+
MeSn3+
MeSnH4-n
MenSnH4-n
Bu3Sn+
BunSnH4-n
BunSnMe4-n
Sn02
SnO2
SnH4
BuSn3+
BuSn3+
Me4SnH4-n
Me4Sn(4-n)+
Me4Sn
Me3Sn+
SnH4
SEDIMENT
INORGANIC
TIN
WATER
ATMOSPHERE
LANDFILL
Me4Sn
+
Me3Sn
2+
Me2Sn
MeSn3+
BuSnH3
Bu2SnH2
EthMe3Sn
Et4Sn
10
Craig and Jenkins
Organometallic compounds in the environment: An overview
11
Microbial demethylation/dealkylation
For some metals, such as mercury and tin, microbial demethylation or dealkylation of organometallic forms are important in detoxication mechanisms. Bacterial
mercury (II) resistance, for example, involves reduction of Hg(II) to Hg(O) via
mercuric reductase (MR). The reduced form of the metal is less toxic, more volatile and is rapidly removed to the atmospheric. Detoxification of organomercurials
proceeds via organomercurial lyase (OL), a product of the Mer B gene, that enzymatically cleaves the Hg-C bond to form Hg(II), which is then removed via mercuric reductase (Gadd 1993; Losi and Frankenberger 1997) (Eqns 4 and 5). For
example
OL
MR
CH3Hg+ → CH4 + Hg2+ →
OL
MR
+
C2H5Hg → C2H6 + Hg2+
Hg0
[4]
→ Hg0
[5]
Oxidative demethylation of methylmercury, involving bacterial liberation of
carbon dioxide, also occurs. The mechanism is thought to involve enzymes associated with bacterial metabolism of C-1 compounds (Oremland et al. 1991) and is
believed to occur widely in freshwater and aqueous environments, under both
aerobic and anaerobic conditions.
Degradation of organotin compounds has been shown for a wide range of microorganisms, including bacteria, fungi and algae (Gadd 2000). Organotin degradation (Eqn.6) is thought to involve sequential cleavage of tin-carbon bonds, resulting in removal of organic groups and a reduction in toxicity (Cooney and
Wuertz 1989; Crompton 1998; Cooney 1988a; Cooney et al. 1988b). Cleavage is
initiated by hydroxo attack (Eqn. 6).
R4 Sn → R3 SnX → R2 SnX 2 → RSnX 3 → SnX 4
[6]
Tributyltin oxide (TBTO) and tributyltin napthenate (TBTN) have been shown
to be degraded by fungal action to di- and monobutyltins. Certain gram-negative
bacteria and the green alga Ankistrodesmuc falcatus can also dealkylate tributyltin,
giving rise to dibutyl-, monobutyl- and inorganic tin products; the alga was able to
metabolise around 50% of the accumulated tributyl over a four-week period
(Maguire 1984). Similar end-products are formed by the action of soil
microorganisms on triphenyltin acetate (Barnes et al. 1973). Tin-carbon bonds are
also cleaved abiotically, for example by UV, and it has been difficult to establish
the relative importance of abiotic and biotic mechanisms of degradation in the
natural environment (Gadd 2000). In some circumstances, environmental conditions (e.g. pH or redox potential), established by microbial activity, strongly
12
Craig and Jenkins
pH or redox potential), established by microbial activity, strongly influence the
extent of abiotic degradation of organotins (Gadd 2000). This discussion relating
to abiotic and biotic organotin degradation also apply to other organometal(loids).
Bacterial demethylation of methylarsenicals is known to occur in aerobic aqueous and terrestrial environments, giving CO2 and arsenate (Andreae et al. 1986).
Several soil bacteria, such as Achromobacter, Flavobacterium and Pseudomonas,
have been shown to possess organoarsenical demethylation ability. Bacterial demethylation of methylarsenic acids excreted by marine algae is an important part
of the biogeochemical cycling of arsenic.
Dimethylselenide has been shown to be demethylated in anaerobic environments by methanogenic and suphate reducing bacteria, producing CO2 and CH4
(Newman et al. 1997). Several bacterial isolates form aerobic soils, - including
members of the genera Pseudomonas, Xanthmononas and Corynebacterium –
have been shown to use methylselenides as sole source of carbon (Doran and
Alexander 1977).
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